Polymerization catalysts,their manufacture and use for polymerizing cyclic ethers

ABSTRACT

A process for manufacturing an improved catalyst comprising reacting an aluminum compound with a zinc compound and contacting the resultant catalyst with a primary alcohol of the general formula R&#39;&#39;-CH2-OH, wherein R&#39;&#39; is a hydrocarbon monovalent radical containing from 1 to 20 carbon atoms.

United States Patent [72] Inventors Maseh Osgan Paris; Robert Charpentier, Epinay, Seine; Philippe Teyssie, Vesinet, all of France [21] Appl. No. 777,893

[22] Filed Nov. 21, 1968 [45] Patented Sept. 21, 1971 [73] Assignee Institut Francais du Petrole des Carburants et Lubrifiants Rueil Malmaison, (Hauts de Seine), France [32] Priority Nov. 21, 1967 [33] France 1 129,123

[52] U.S.Cl 252/431 C, 260/2 A 511 1m.c| C08g 23 14 [50] Field of Search 252/43 I [56] References Cited UNITED STATES PATENTS 3,313,846 4/]967 Slovinsky 252/431 X 3,427,260 2/1969 Maguet-Martin et al. 252/431 X Primary ExaminerPatrick P. Garvin Att0rneyCraig, Antonelli and Hill ABSTRACT: A process for manufacturing an improved catalyst comprising reacting an aluminum compound with a zinc compound and contacting the resultant catalyst with a primary alcohol of the general formula R'-CH -OH, wherein R is a hydrocarbon monovalent radical containing from 1 to 20 carbon atoms.

POLYMERIZATION CATALYSTS, THEIR MANUFACTURE AND USE FOR POLYMERIZING CYCLIC ETHERS The present invention relates to improvements in the manufacture and use of the polymerization catalysts previously described in Belgian Pat. No. 680,456 in the name of the ap plicant and U.S. Pat. No. 3,432,445. These catalysts are obtainedB eactingatrivalent metal compound of the formula:

Rr-O

with a divalent metal compound of the fonnula:

Y O M Z (B) wherein M is a trivalent metal, M a divalent metal, Z represents the radical OR or an acyloxy radical, one of the radicals X and Y being a radical R and the other an acyl radical, the radicals R to R being hydrocarbon monovalent radicals, a byproduct of formula XOY being separated during the reaction.

There are generally used from 0.01 to 100 (preferably from 0.1 to moles of compound A per mole of compound B. Further details are given in the specification of the Belgian Pat. No. 680,456, published Dutch application No. 66/6,207 or U.S. Pat. No. 3,432,445.

The new feature, object of the present invention, consists of treating the catalyst with a primary alcohol containing at least two carbon atoms per molecule, which treatment results in an unexpected improvement in the activity of the catalyst, far higher than that achieved in the case of a treatment with a secondary or tertiary alcohol, said improvement being observed in the form of a higher reaction velocity and/or of an increase in the proportion of the stereoregular portion of the obtained polymer. It has thus been observed that whereas, in some cases, in the presence of the previous catalyst as defined in the Belgian Pat. No. 680,456 or U.S. Pat. No. 3,432,445,

not result in the mere exchange of a radical in the catalytic complex since in case of operation with an excess of primary alcohol it is observed that the amount of recovered alcohol (corresponding to the alcoholate which has been used for the synthesis of the catalyst) is less than that of the consumed primary alcohol.

Furthermore, if the significant improvement due to the treatment with a primary alcohol, were the result of a mere exchange of radical, an identical improvement should be ob- .tained by introducing this radical in the early stage of the synthesis of the basic catalyst, by use of the trivalent metal in the form of the alcoholate of the primary alcohol.

In fact the experience has shown that the treatment with a primary alcohol of such a catalyst, obtained from an alcoholate of primary alcohol, provided for an astonishing improvement in the properties of said catalyst, which proves that these particular properties were not attributable to the only presence of this radical of primary alcohol.

The preparation of the new catalyst, which consists of contacting the above-defined catalyst with a primary alcohol introduced either in a liquid or vapor state, may be carried out either with or without solvent. Preferably the operation is conducted in a substantially anhydrous medium.

The primary alcohol preferably complies with the general formula R'CH OH wherein R represents a hydrocarbon monovalent radical, preferably containing from one to 20 carbon atoms, such as, for example an alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl, arylalkenyl, alkaryl or alkenylaryl radical. The more currently used alcohols are thosehaving an alkyl radical such as, for instance n-propyl, ri-butyl alcohols and 3-methyl-l-butanol.

As other examples are to be mentioned the following alcohols: l-dodecanol, l-hexa-decanol, 2 propene-lol, as well as benzyl alcohol and 2-phenyl- 1 ethanol.

The amount of primary alcohol introduced must be in the proportion of at least 0.0] mole of alcohol per gram-atom of trivalent metal and preferably between 0.05 and 25 moles of alcohol per gram-atom of trivalent metal of the catalyst, these limits being however not limitative. It is also possible to use a large excess of alcohol which will then act as solvent.

The mixture is brought to a temperature which may, for instance, be comprised between 30 C. and 250 C. and preferably between 10 C. and 180 C., and the time of contact may vary within very wide limits of from a few seconds (for instance 5 seconds) up to several days, according to the desired catalytic properties. it is preferable in certain cases to evaporate the volatile products during and/or after the reaction.

According to a particular embodiment of the invention the basic catalyst is subjected, prior to the introduction of the primary alcohol, to a thermal treatment over a duration of from a few seconds to a few days, the temperature of this treatment being, for example, comprised between 150C. and 300 C.

An improved feature of the present invention consists of having the above-mentioned treatment of the catalyst with a primary alcohol followed with a complementary treatment by a tertiary alcohol or by methanol, under general conditions similar to those described with respect to the treatment with the primary alcohol.

The catalyst obtained as a result of this complementary treatment exhibits the advantage of keeping a high degree of activity at the low concentrations at which the normal catalyst loses a part of its activity.

Moreover, due to this complementary treatment, there are obtained polymers whose insoluble portion in acetone at 20 C. is substantially higher.

As examples of preferred tertiary alcohols are to be mentioned tert.butanol, tert.pcntanol, tert.octanol as well as other saturated aliphatic tertiary alcohols.

The following examples are given for illustrative purposes and are not intended to limit in any way the scope of the invention. Comparative examples 1 bis, 4A, 4B, 4C and l lB are not however within the scope of the invention. In all of these examples temperatures are in degrees centigrades.

EXAMPLE I Into a reactor previously purged with dry argon, and provided with a reflux condenser, an outlet and a stirrer, there is placed under argon atmosphere a solution containing 0.3 gram-atom of catalyst as manufactured according to the process described in Belgian Pat. No. 680,456 or U.S. Pat. No. 3,432,445 in l50 cc. ofchlorobenzene.

The above-mentioned catalyst has been obtained from aluminum tri-n-butoxide and zinc acetate. The amount of catalyst is expressed in term of the total of the trivalent metal and the divalent metal (atomic ratio Al/Zn=2) contained therein, given in gram-atoms.

To this solution are added g. of dry n-butyl alcohol and the mixture is treated to reflux for 8 hours. The mixture is then allowed to cool down to the ambient temperature and the excess of alcohol and chlorobenzene are distilled off under reduced pressure so as to eliminate volatile substances. Distillation begins at the ambient temperature under a pressure of about 1 torr and terminates with a temperature of about 50 C. (bath temperature) and a pressure of about 0.05 torr. Thereafter the resinous residue is dissolved in about 20 cc. of chlorobenzene and distilled again in the manner hereabove set forth.

This operation is repeated three or four times, so as to completely remove, by carrying away, the free alcohol traces remaining in the residues.

The residue is thereafter dissolved in dry heptane and there is so obtained a limpid yellow solution, exhibiting a green fluorescence, which is kept under argon atmosphere. The

results of the polymerization tests with the use of the obtained catalytic solution, as well as with any of the solutions whose preparation is described in example 2 to 4C, are given in table l hereafter.

EXAMPLE 1 bis A catalyst is prepared according to the process of example 1 except that it is not subjected to the treatment with a primary alcohol. Results are shown in table I.

EXAMPLE 2 A The apparatus used is the same as in example 1 except for the following changes: the reflux condenser is replaced by a rectifying column of the Vigreux-type, comprising a distillation head permitting either to effect a partial or complete distillation, or to maintain the reaction under condition of total reflux. in the above-described apparatus there are introduced 200 cc. of a solution of catalyst in decahydronaphthalene, reaction solvent which is not subjected to distillation after termination of the catalyst preparation (in accordance with the method described in Belgian Pat. No. 680,456 or US. Pat. No. 3,432,445). This solution, prepared from aluminum triisopropoxide and anhydrous zinc acetate, contains 0.132 gram-atom of catalyst (Al+Zn). and 150 cc. of n-butyl alcohol are added thereto.

The mixture is heated to total reflux and it is observed that the temperature at the top of the column (83) is the distillation temperature of isopropyl alcohol.

All of the isopropyl alcohol is thus recovered by distillation with partial reflux (about l ccJminute). The distillation is then continued and the temperature rises to ll8-l 19 C.; there is further recovered from to 10 cc. of liquid having distilled off at said temperature. The operation is thereafter identical to that described in example 1. The heptane solution of the resulting catalyst is referenced 2A.

EXAMPLE 28 Example 2A is repeated with the exception of the following change: The operation is conducted from the beginning under reduced pressure (about 1 to 2 torrs), whereas the mixture (catalyst n-butyl alcohol) is heated to 45 C. during the whole time of operation which otherwise is continued in the same manner as in example 1.

EXAMPLE 2C Example 2A is repeated except that, after distillation of the displaced isopropyl alcohol the distillation is stopped. The whole mixture is heated to reflux for 8 hours under atmospheric pressure. The operation is thereafter continued similarly as according to example 1.

EXAMPLES 3A, 3B and 3C 'Alum'inum triisopropoxide is condensed with zinc acetate according to the operating manner described in example 1 of Belgian Pat. No. 680,456 with the exception of the following changes: the condensation is carried out in tetrahydronaphthalene instead of decahydronaphthalene. After removal of the isopropyl acetate formed by distillation, treating of the condensate is continued for 5 hours at 200-** C.

After cooling there is observed the formation of a precipitate in substantial amount. To this mixture are added 400 g. of n-butyl alcohol per gram-atom of aluminum. After stirring for'a short time it is observed that the insoluble portion becomes dissolved in the form of a homogeneous yellow solutron.

The same operations as in examples 2A, 2B and 2C are then carried out with the above solution.

EXAMPLES 4A and 4C For comparison purposes the workable conditions of examples 2A and 3C are repeated except that isopropyl alcohol is substituted for n-butyl alcohol.

It is observed that the dissolution is not complete with isopropyl alcohol as it is in example 3C with butyl alcohol, and that, after heating at reflux for 8 hours, it still remains an insoluble portion. After decantation of the insoluble portion, the soluble portion is transferred into a receiver purged with argon. The complexometric analysis shows that the atomic ratio Al/Zn, which is equal to 2 at the starting time, is brought to 3; this solution is given reference 4C.

The analysis of the insoluble portion shows that is consists essentially of zinc isopropylate.

On the contrary there is obtained a substantially homogeneous and limpid solution when using the operating conditions of example 2A, the atomic ratio Al/Zn being maintained at the starting value i.e. equal to 2. This solution is given reference 4A.

EXAMPLE 48 Example 4C is repeated but with the use, as alcohol, of secondary butyl alcohol. There is thus obtained a homogenous, limpid solution to which is given reference 48.

POLYMERIZATION TESTS The operating conditions have been the following:

monomer: propylene oxide in an amount of 58 parts by weight.

solvent: n-heptane, 640 parts by weight catalyst: 0.025 gram-atom of metal (Al+Zn) (for 58 g. of

propylene oxide) Polymerization is continued for 1 hour at 50 C. and is stopped by addition of 0.5 part by weight of aniline. The polymer is separated by evaporation of the solution in a stream of air at ambient temperature.

The results of the operations carried out with each of the catalysts of examples 1 to 4C are given in the following table:

In these examples there are used the same operating conditions as in example 3C but the primary alcohol is changed.

There are used 5 gram-molecules of the selected primary alcohol per each gram-atom of aluminum.

At the end of each operation there is obtained a resinous product which is completely soluble in anhydrous heptane, except in the case of example 8. In said last-mentioned example wherein the selected primary alcohol is benzyl alcohol, the final product exhibits a very low solubility in heptane and it is dissolved in anhydrous toluene in which it is very soluble.

The results as well as the corresponding polymerization tests are given in table Il below.

TABLE II EXAMPLE l4 Polymerization tests are carried out with the catalysts ob tained according to examples 2A and 1 1A to 13. The Exam? 5 polymerization conditions are identical to those described use, zrcypmypmpanc after example 48, except for the catal st concentration q, wnvmiun chosen equal to 0.010 gram-atom of metal Al+Zn) per 58 g. in polymer of propylene oxide, and for the duration of the polymerization.

5 n pf0pyitoluene $6 The results are given in table lll below: alcohol s imhulyl chlumhcn- 37 alcohol IJJIIL 7 n uclyl 'l'HNlolucm: 04

alcohol (2.1) 24 flhenyl -chloru l0 ethyl alc. naphthalene Catalyst Duration Ki conversion Ki ehlorobenaccording to of the to polymer insoluble lun examplc No. polymerin acetone (2: l) ization at 20 C.

THN tetrahydronaphthalene polymerization solvent 2 A 70 62 toluene (815 parts by weight) II A 72 H a 24 60 13 1.5 so 90 The polymerization conditions, except for example 8 wherein the solvent is toluene, are those of examples 1 to 4C. 25 7 EXAMPLE 9 What is claimed as this invention is: 1. An improved process for manufacturing catalysts comof anylglycldyl ether 52 of n'heptane and 0'008 prising reacting a trivalent metal compound ofthe formula atom (AH-Zn) of the catalyst of example 3, are heated under stirring at 50 C. for 16 hours. The polymerization is stopped R10 by addition of 0.1 g. of aniline and 0.05 g. of N-phenyl-B- naphthyl-amine.

The solvent is evaporated by means of an air stream and R finally the resulting polymer is dried at 70 C. in a vacuum drye i g p g g h with a compound of divalent metal Y-O-M-Z, wherein M is T ere are 0 0 a w my p0 ymer w aluminum, M is zinc, Z is a hydrocarbon acyloxy radical, X is rsporids to a cimveislon rate of p The mmnslc R.,, Y is a hydrocarbon acyl radical, R to R radicals being viscosity, determined in toluene at 30 C. attains 2.3 dl./g. hydrocarbon monovalem radicals Said improved process EXAMPLE 0 40 comprising the additional step of further contacting the resulting catalyst with a primary alcohol of the general formula 12 of phenylglycldyletheri 51 gof hcplane and 0-008 R'CH OH, wherein R is a hydrocarbon monovalent radical gram-atom H' 0f the Catalyst of example 3C, are heated containing from one to 20 carbon atoms, at a temperature of under stirring, at 50 C. for 85 minutes. The polymerization is bctwecn 3 and 250 C Said alcohol being present in an pp by addition of of anillne- The resulting insoluble amount of at least 0.01 mole per gram-atom of trivalent metal polymer is filtered, washed with toluene and then dried at 60 in the cata|ySL 3 reduced Pressure of for 18 hours- The 2. A process according to claim 1 characterized in that the ferential thermal analysis shows a melting point of 202.7 C. alcohol is an alkanoL 3. A process according to claim 1 wherein there are used EXAMPLE H A from 0.05 to 25 moles of primary alcohol per gram-atom of There are heated 0.10 gram-atom of the catalyst obtained trivalent metal in the talyst. according to example 2A (this catalyst has been treated with A process d ng to claim 1 wherein the resulting nbutyl alcohol) with 200 g. of tertiary amyl alcohol admixed catalyst is thereafter treated with methanol or with a saturated with 300 cc. of chlorobenzene, for 7 hours at 100 C. (bath allphatlc hydrocarbon tertiary alcohol. i temperature) under the autogenous pressure (about 1.5 bars). The P Q Claim Wherem the p i ry h l I m- The operating conditions are thereafter the same as in examroduccd in a liquid or vapor state. i 1 6. The process of claim 1, wherein R is selected from the group consisting of an alkyl, an alkenyl, an aryl, and an arylal- EXAMPLE 11 B kyl radical. By way of comparison the preceding example is repeated fg ig of clam f h the pnmarly 3 5 with the exception ofthe treatment with n-butyl alcohol. Se ec e mm 6 group Cons mg 0 n-propano mane 3-methyl-l-butanol, l-dodecanol, l-hexa-decanol, 2 propene- EXAMPLE 12 1-01, 2-phenyl-l'ethanol and benzyl alcohol. 8. The process of claim 1, wherein the resulting catalyst is A :atalyst P p 'f P to example 1 1A except contacted with the primary alcohol at a temperature of that tertiary amyl alcohol lS used in proportion of only 8.8 g. between and 0 P gram'atom of catalyst 9. The process of claim 1, wherein prior to the introduction of the primary alcohol the catalyst is subjected to a thermal EXAMPLE 13 treatment at a temperature between 150 and 300 C. A catalyst is prepared according to example 12 except that tertiary butyl alcohol is used in lieu of tertiary amyl alcohol. 

2. A process according to claim 1 characterized in that the alcohol is an alkanol.
 3. A process according to claim 1 wherein there are used from 0.05 to 25 moles of primary alcohol per gram-atom of trivalent metal in the catalyst.
 4. A process according to claim 1 wherein the resulting catalyst is thereafter treated with methanol or with a saturated aliphatic hydrocarbon tertiary alcohol.
 5. The process of claim 1, wherein the primary alcohol is introduced in a liquid or vapor state.
 6. The process of claim 1, wherein R'' is selected from the group consisting of an alkyl, an alkenyl, an aryl, and an arylalkyl radical.
 7. The process of claim 1, wherein the primary alcohol is selected from the group consisting of n-propanol, n-butanol, 3-methyl-1-butanol, 1-dodecanol, 1-hexa-decanol, 2 propene-1-ol, 2-phenyl-1-ethanol and benzyl alcohol.
 8. The process of claim 1, wherein the resulting catalyst is contacted with the primary alcohol at a temperature of between -10* C. and 180* C.
 9. The process of claim 1, wherein prior to the introduction of the primary alcohol the catalyst is subjected to a thermal treatment at a temperature between 150* and 300* C. 